Crosslinked microgel for cathodic electrocoating compositions

ABSTRACT

A cationic finely divided polymeric microgel dispersed in an aqueous medium for use in cationic electrocoating compositions of a epoxy terminated polyepoxy hydroxy ether resin being end capped with a ketimine, a primary amine, secondary amine or mixtures thereof and amino siloxane to provide silanol groups and amino groups; the amino groups of the polymeric microgel being neutralized with an acid to form cationic groups for water dispersibility and the silanol groups being condensed with hydroxy groups of the resins and other silanol groups of the resin thereby forming a crosslinked microgel.

BACKGROUND OF THE INVENTION

This invention is directed to microgels and in particular to microgels that are useful in cathodic electrocoating compositions.

The coating of electrically conductive substrates by an electrodeposition process (also called an electrocoating process) is a well known and important industrial process. Electrodeposition of primers to automotive substrates is widely used in the automotive industry. In this process, a conductive article, such as an autobody or an auto part, is immersed in a bath of a coating composition of an aqueous emulsion of film forming polymer and acts as an electrode in the electrodeposition process. An electric current is passed between the article and a counter-electrode in electrical contact with the aqueous emulsion, until a coating having the desired thickness is deposited on the article. In a cathodic electrocoating process, the article to be coated is the cathode and the counter-electrode is the anode.

Resin compositions used in the bath of a typical cathodic electrodeposition process also are well known in the art. These resins typically are made from polyepoxide resins which have been chain extended and then an adduct is formed to include amine groups in the resin. Amine groups typically are introduced through reaction of the resin with an amine compound. These resins are blended with a crosslinking agent and then neutralized with an acid to form a water emulsion which is usually referred to as a principal emulsion.

The principal emulsion is combined with a pigment paste, coalescent solvents, water, and other additives to form the electrocoating bath. The electrocoating bath is placed in an insulated tank containing the anode. The article to be coated is the cathode and is passed through the tank containing the electrocoating bath. The thickness of the coating that is deposited on the article being electrocoated is a function of the bath characteristics, the electrical operating characteristics, the immersion time, and the like.

The resulting coated article is removed from the bath after a set period of time and is rinsed with deionized water. The coating on the article is cured typically in an oven at sufficient temperature to produce a crosslinked finish on the article.

Cathodic electrocoating compositions, resin compositions, coating baths, and cathodic electrodeposition processes are disclosed in Jerabek et al U.S. Pat. No. 3,922,253 issued Nov. 25, 1975; Wismer et al U.S. Pat. No. 4,419,467 issued Dec. 6, 1983; Belanger U.S. Pat. No. 4,137,140 issued Jan. 30, 1979, Wismer et al U.S. Pat. No. 4,468,307 issued Aug. 25, 1984 and DebRoy et al U.S. Pat. No. 5,070,149 issued Dec. 3, 1991.

The use of cationic microgels in cathodic electrocoating compositions is known to solve problems of improving edge coverage and reducing edge corrosion as shown in Abbey et al U.S. Pat. No. 4,525,260 issued Jun. 25, 1985, Tsuchiya et al U.S. Pat. No. 4,788,246 issued Nov. 29 1988, Shibata et al U.S. Pat. No. 4,987,178 issued Jan. 22, 1991 and Corrigan et al U.S. Pat. No. 5,096,556 issued Mar. 17, 1992.

However, Abbey et al and Shibata et al are both directed to acrylic polymer based microgels and Tsuchiya et al is directed to a polybutadiene based microgel. Microgels based on acrylic polymers or butadiene polymers adversely affect the general corrosion protection of coatings formed from cathodic electrocoating compositions. The microgel of this invention is based on an epoxyhydroxy polyether resin and does not reduce the general corrosion protection of coatings formed from cathodic electrocoating compositions. Corrigan et al forms microgels based on epoxy resins but uses a different and less efficient synthesis for forming microgels and forms microgels having a different chemical structure from those of the invention.

SUMMARY OF THE INVENTION

A cationic finely divided polymeric microgel dispersed in an aqueous medium for use in cationic electrocoating compositions of an epoxy terminated polyepoxy hydroxy ether resin being end capped with a ketimine, a primary or secondary amine or mixtures of any of these and amino silane to provide silanol groups and amino groups; the amino groups of the polymeric microgel being neutralized with an acid to form cationic groups for water dispersibility and the silanol groups being condensed with hydroxy groups of the resin and other silanol groups of the resin thereby forming a crosslinked microgel.

A process for forming the microgel and cationic electrocoating compositions containing the microgel also are a part of this invention.

DETAILED DESCRIPTION OF THE INVENTION

The microgel of this invention when added to a conventional electrocoating composition improves the edge corrosion of the electrocoating composition and provides thicker edge coverage in comparison to conventional electrocoating compositions that do not contain microgel. The microgel does not adversely affect other properties of the electrocoating composition such as its overall corrosion protection. The microgel can be added directly to an electrocoating tank containing an epoxy based composition and need not be formulated with the coating composition. The microgel usually is added to the electrocoating composition in amounts of about 0.1-20% by weight, based on the weight of the binder of the coating composition to achieve these improved results.

The microgel is prepared by reacting the terminal groups of an epoxy terminated polyepoxy hydroxy ether resin with a ketimine or a primary or secondary amine or mixtures thereof and amino silane to form an end capped resin having silanol groups and amino groups. The amino groups of the resin are neutralized with an acid to form cationic groups that are water dispersible and the resin is dispersed in water and the silanol groups condense with hydroxy groups of the resins and other silanol groups to form a crosslinked microgel particles that are dispersed in water and form an emulsion.

The epoxy terminated polyepoxy hydroxy ether resin used to form the microgel have a 1,2-epoxy equivalency of about two or more, that is, polyepoxides which have on an average basis two or more epoxy groups per molecule. The preferred polyepoxides are polyglycidyl ethers of cyclic polyols. Particularly preferred are polyglycidyl ethers of polyhydric phenols such as bisphenol A. These polyepoxides can be produced by etherification of polyhydric phenols with epihalohydrin or dihalohydrin such as epichlorohydrin or dichlorohydrin in the presence of alkali. Examples of polyhydric phenols are 2,2-bis-(4-hydroxyphenyl)ethane, 2-methyl-1,1-bis-(4-hydroxyphenyl) propane, 2,2-bis-(4-hydroxy-3-tertiarybutylphenyl)propane, 1,1-bis-(4-hydroxyphenol)ethane, bis-(2-hydroxynaphthyl)methane, 1,5-dihydroxy-3-naphthalene or the like.

Besides polyhydric phenols, other cyclic polyols can be used in preparing the polyglycidyl ethers of cyclic polyol derivatives. Examples of other cyclic polyols would be alicyclic polyols, particularly cycloaliphatic polyols, such as 1,2-bis(hydroxymethyl)cyclohexane, 1,3-bis(hydroxymethyl)cyclohexane, 1,2 cyclohexane diol, 1,4 cyclohexane diol and hydrogenated bisphenol A.

The polyepoxides have molecular weights of at least 200 and preferably within the range of 200 to 3000, and more preferably about 340 to 2000.

The polyepoxides can be chain extended with a polyether or a polyester polyol which enhances flow and coalescence. Typical useful chain extenders are polyols such as polycaprolactone diols such as Tone 200® series available from Union Carbide Corporation, polyoxypropylene diamine such as Jeffamine D-2000® having a molecular weight of about 2000 available from Texaco Chemical Company and ethyoxylated Bisphenol A such as SYNFAC 8009® available from Milliken Chemical Company.

Examples of polyether polyols and conditions for chain extension are disclosed in U.S. Patent No. 4,468,307. Examples of polyester polyols for chain extension are disclosed in Marchetti et al U.S. Patent No. 4,148,772 issued Apr. 10, 1979.

The terminal epoxy groups of the epoxy hydroxy polyether resin are reacted with a ketimine or a primary or secondary amine or a mixture thereof and with an amino silane. Generally about 20-90% of the epoxy or glycidyl groups are reacted with the ketimine or primary or secondary amine or the mixture and 10-80% of the epoxy groups are reacted with amino silane. The reaction is at about 25° to 45° C. for about 15 to 60 minutes.

Ketimines useful in this invention are formed from ketones and primary amines. The water formed is removed, for example, by azeotropic distillation. Useful ketones include dialkyl, diaryl and alkylaryl ketones having 3-13 carbons atoms. Specific examples include acetone, methyl ethyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, methyl aryl ketone, ethylisomyl ketone, ethyl amyl ketone, acetophenone, and benzophenone. Suitable diamines are ethylene diamine, 1,3-diamopropane, 1,4-diaminobutane, 1,6-diaminohexane, 4,9-dioxadodecone, 1, 12-diamine and the like. One typically useful ketimine is diketimine (ketimine of diethylene triamine and methyl isobutyl ketone).

Typically useful primary and secondary amines are diethyl amine, methyl ethyl amine, methyl ethanol amine, ethyl ethanol amine, mono ethanol amine, ethyl amine, dimethyl amine, diethyl amine, propyl amine, dipropyl amine, isopropyl amine, diisopropyl amine, butyl amine, dibutyl amine and the like.

Typically useful amino silanes are amino alkyl trialkoxy silanes such as gamma-amino propyl trimethoxy silane, gamma-amino propyl triethoxy silane, gamma-amino propyl tripropoxy silane, N-beta(amino ethanol)gamma amino propyl trimethoxy silane and the like. Gamma-amino-propyl trimethoxy silane is preferred for a high quality microgel.

Typical acids used to neutralize the hydroxy and amino groups of the resin to form cationic groups which are water dispersible are lactic acid, acetic acid and formic acid.

When the resin is inverted into water the silanol groups condense with the hydroxyl groups and other silanol groups on the resin and a stable dispersion of microgel particles are formed having a particle size of 0.01 to 6 microns determined by a Coulter Model LS150 Automated Laser Based Particle Size Analyzer made by Coulter Scientific Instruments.

A surfactant may be used in an amount of up to 5% by weight of the microgel in the composition to keep the particles dispersed. Typically useful surfactants are described hereinafter.

The microgel is designed for use in cathodic electrocoating compositions but could be used in other waterbased compositions such as aqueous latexes and enamels.

Typical cationic electrocoating compositions are shown in DebRoy et al U.S. Pat. No. 5,070,149 issued Dec. 3, 1991 and the aforementioned U.S. Pat. Nos. 3,922,253, 4,419,467, 4,137,140 and 4,468,307.

These cationic electrocoating compositions typically contain a cationic resinous binder of an epoxy/amine adduct and a blocked isocyanate crosslinking agent and are present in amounts of about 30-50% by weight of solids.

Besides the ingredients described above, the electrocoating compositions usually contain a pigment which is incorporated into the composition in the form of a paste. The pigment paste is prepared by grinding or dispersing a pigment into a grinding vehicle and optional ingredients such as wetting agents, surfactants, and defoamers. Pigment grinding vehicles are well known in the art. After grinding, the particle size of the pigment should be as small as practical, generally, a Hegman grinding gauge of about 6 to 8 is usually employed.

Pigments which can be employed in the practice of the invention include titanium dioxide, basic lead silicate, strontium chromate, carbon black, iron oxide, clay and so forth. Pigments with high surface areas and oil absorbencies should be used judiciously because they can have an undesirable effect on coalescence and flow.

The pigment-to-resin weight ratio is also important and should be preferbly less than 50: 100, more preferably less than 40: 100, and usually about 20 to 40: 100. Higher pigment-to-resin solids weight ratios also have been found to adversely affect coalescence and flow.

The coating compositions of the invention can contain optional ingredients such as wetting agents, surfactants, defoamers and the like. Examples of surfactants and wetting agents include alkyl imidazolines such as those available from Ciba-Geigy Industrial Chemicals as Amine C®, acetylenic alcohols available from Air Products and Chemicals as Surfynol 104®. These optional ingredients, when present, constitute from about 0 to 20 percent by weight of resin solds. Plasticizers promoting flow are optional ingredients. Examples of plasticizers are high boiling water immiscible materials such as ethylene or propylene oxide adducts of nonyl phenols or bisphenol A. Plasticizers can be used at levels of up to about 15 percent by weight resin solids.

Curing catalysts such as tin catalysts are usually present in the composition. Examples are dibutyltin dilaurate and dibutyltin oxide. When used, they are typically present in amounts of about 0.05 to 2 percent by weight tin, based on weight of total resin solids.

The electrodepositable coating compositions of the present invention are dispersed in aqueous medium. The term "dispersion" as used within the context of the present invention is believed to be a two-phase translucent or opaque aqueous resinous system in which the resin is in the dispersed phase and water the continuous phase. The average particle size diameter of the resinous phase is about 0.1 to 10 microns, preferbly less than 5 microns. The concentration of the resinous products in the aqueous medium is, in general, not critical, but ordinarily the major portion of the aqueous dispersion is water. The aqueous dispersion usually contains from about 3 to 50 percent preferably 5 to 40 percent by weight resin solids. Aqueous resin concentrates which are to be further diluted with water, generally range from 10 to 30 percent by total weight solids.

Besides water, the aqueous medium may also contain a coalescing solvent. Useful coalescing solvents include hydrocarbons, alcohols, esters, ethers and ketones. The preferred coalescing solvents include alcohols, polyols and ketones. Specific coalescing solvents include monobutyl and monohexyl ethers of ethylene glycol, and phenyl ether of propylene glycol. The amount of coalescing solvent is not unduly critical and is generally between about 0 to 15 percent by weight, preferably about 0.5 to 5 percent by weight based on total weight of the resin solids.

In the electrocoating process, a film is electrodeposited on a metal substrate using a voltage of about 50 to 500 volts and the resulting film is baked at about 120° to 250° C. for about 10 to 60 minutes to form a film about 15 to 60 microns in thickness.

The following examples illustrate the invention. All parts and percentages are on a weight basis unless otherwise specified.

EXAMPLES Example 1

A microgel was prepared by charging the following constituents into a reactor equipped with a reflux condenser, heat source, a stirrer and a thermometer:

    ______________________________________                                                                Parts by Weight                                         ______________________________________                                         Portion 1                                                                      epoxy resin of diglycidyl ether of                                                                      1005.80                                               Bisphenol A from Shell Chemical Company                                        having an equivalent weight of 188                                             Tone 200 ® polycaprolactone diol from Union                                                         389.90                                                Carbide Corporation                                                            Bisphenol A              289.20                                                Xylene                   81.70                                                 Portion 2                                                                      Dimethyl benzyl amine    1.70                                                  Portion 3                                                                      Dimethyl benzyl amine    3.41                                                  Portion 4                                                                      Blocked isocyanate crosslinker solution - 40.3                                                          1515.40                                               parts, hexyl Cellosolve, 12.2 parts trimethylol                                propane, 47.5 parts toluene diisocyante, 90.0                                  parts methyl isobutyl ketone and 10 parts                                      butanol                                                                        Portion 5                                                                      Methylethanol amine      94.60                                                 A1100 - gamma Aminopropyltriethoxy silane                                                               70.80                                                 Portion 6                                                                      Lactic acid              80.60                                                 Surfactant - 120 parts Amine C ® from Ciba                                                          27.80                                                 Geigy Inc., 120 parts acetylenic alcohol avail-                                able as Surfynol 104 ® from Air Products and                               Chemicals, Inc., 120 parts of 1-butoxy ethanol,                                221 parts of deionized water and 19 parts glacial                              acetic acid                                                                    Dibutyl tin dilaurate    4.00                                                  Deionized water          4836.30                                                 Total                  8401.21                                               ______________________________________                                    

Portion 1 was charged into the reaction vessel heated to about 146° C. under a blanket of nitrogen with constant stirring and the Portion 2 was added. The reaction mixture was held at about 160° C. for about 1 hour after there was a peak exotherm of the reaction. The reaction mixture was cooled to about 146° C. and then Portion 3 was added and the epoxide equivalent weight was advanced to 1050 to form a polymer solution. Portion 4 was added to cool the reaction mixture below 105° C. Portion 5 was added and the reaction mixture was held at 120° C. for 1 hour. Portion 6 was charged into a separate vessel and mixed. The above reaction mixture was added to Portion 6 and then held under agitation for 8 hours.

The resulting microgel emulsion had a solids content of about 24.32%. The particle size of the emulsion was determined as described above and was 0.246 microns. The microgel had about 50% of the amine functionality neutralized with acid and 80% of the epoxy end groups capped with methyl ethanol amine and 20% of the end groups capped with amino silane. The percent of insoluble microgel was determined by solvent extraction techniques and was 71.52%.

Example 2

The following constituents were changed into a reaction vessel equipped with a reflux condenser, a heat source, thermometer and a stirrer:

    ______________________________________                                                                Parts by Weight                                         ______________________________________                                         Portion 1                                                                      Bisphenol A              489.00                                                described in Example 1   1255.00                                               Xylene                   67.00                                                 Portion 2                                                                      Dimethyl benzyl amine    1.20                                                  Portion 3                                                                      Methyl isobutyl ketone   490.00                                                Blocked isocyanate crosslinker solution -                                                               816.00                                                described in Example 1                                                         Portion 4                                                                      Diketimine               505.00                                                A1100 - amino silane described in Example 1                                                             89.500                                                Portion 5                                                                      Lactic acid              221.00                                                Surfactant - described in Example 1                                                                     60.00                                                 Dibutyl tin dilaurate    4.45                                                  Deionized water          4321.00                                                 Total                  8319.15                                               ______________________________________                                    

Portion 1 was charged into the reaction vessel heated to about 146° C. under a blanket of nitrogen with constant stirring and then Portion 2 was added. The reaction mixture was held at about 160° C. for about 1 hour after there was a peak exotherm of the reaction. The reaction mixture was cooled to about 77° C. and then Portion 3 was added and mixed for 5 minutes and then Portion 4 was added. The reaction was kept below 115° C. and held for about 30 minutes to form a polymer solution. Portion 5 was charged into a separate vessel and heat to 71° C. with constant mixing. The above polymer solution was added to mixed Portion 5 and held under agitation for 8 hours.

The resulting microgel emulsion had a solids content of about 38.51%. The particle size of the emulsion was determined as described above and was 0.188 microns. The microgel had about 44% of the amine functionality acid neutralized and 80% of the epoxy end groups capped with diketimine and 20% of the end groups capped with amino silane. The percent of insoluble microgel was determined by solvent extraction techniques and was 69.65%. cl Example 3

The following constituents were charged into a reaction vessel equipped with a reflux condenser, a heat source, thermometer and a stirrer:

    ______________________________________                                                                Parts by Weight                                         ______________________________________                                         Portion 1                                                                      Bisphenol A              171.00                                                described in Example 1   458.70                                                Xylene                   34.00                                                 Portion 2                                                                      Dimethyl benzyl amine    2.50                                                  Portion 3                                                                      Methyl isobutyl ketone   80.00                                                 Portion 4                                                                      Methylethanol amine      14.10                                                 Diketimine               240.70                                                A1100 - amino silane described in Example 1                                                             19.90                                                 Portion 5                                                                      Lactic acid              96.90                                                 Surfactant - described in Example 1                                                                     19.00                                                 Dibutyl tin dilaurate    4.40                                                  Deionized water          2006.00                                                 Total                  3147.20                                               ______________________________________                                    

Portion 1 was charged into the reaction vessel heated to about 146° C. under a blanket of nitrogen with constant stirring and then Portion 2 was added. The reaction mixture was held at about 160° C. for about 1 hour after there was a peak exotherm of the reaction. The reaction mixture was cooled to about 77° C. and then Portion 3 was added and mixed for 5 minutes and then Portion 4 was added. The reaction was kept below 115° C. and held for about 30 minutes to form a polymer solution. Portion 5 was charged into a separate vessel and heat to 71° C. with constant mixing. The above polymer solution was added to mixed Portion 5 and held under agitation for 8 hours.

The resulting microgel emulsion had a solids content of about 17.19%. The particle size of the emulsion was determined as described above and was 0.087 microns. The microgel had about 42.6% of the amine functionality acid neutralized and 70% of the epoxy end groups capped with diketimine and 20% of the end groups capped with methylethanol amine and 10% of the end groups capped with amino silane. The percent of insoluble microgel was determined by solvent extraction techniques and was 75.27%.

Example 4

The following constituents were charged into a reaction vessel equipped with a reflux condenser, a heat source, thermometer and a stirrer:

    ______________________________________                                                                Parts by Weight                                         ______________________________________                                         Portion 1                                                                      Bisphenol A              490.00                                                described in Example 1   1255.00                                               Xylene                   67.00                                                 Portion 2                                                                      Dimethyl benzyl amine    1.20                                                  Portion 3                                                                      Blocked isocyanate crosslinker solution -                                                               761.60                                                described in Example 1                                                         Portion 4                                                                      Diketimine               475.80                                                A1100 - amino silane described in Example 1                                                             221.40                                                Portion 5                                                                      Lactic acid              220.30                                                Surfactant - described in Example 1                                                                     37.80                                                 Dibutyl tin dilaurate    4.40                                                  Deionized water          5221.60                                                 Total                  8756.10                                               ______________________________________                                    

Portion 1 was charged into the reaction vessel heated to about 146° C. under a blanket of nitrogen with constant stirring and the Portion 2 was added. The reaction mixture was held at about 160° C. for about 1 hour after there was a peak exotherm of the reaction. The reaction mixture was cooled to about 77° C. and the Portion 3 was added and mixed for 5 minutes and then Portion 4 was added. The reaction was kept below 115° C. and held for about 30 minutes to form a polymer solution. Portion 5 was charged into a separate vessel and heated to 71° C. with constant mixing. The above polymer solution was added to mixed Portion 5 and held under agitation for 8 hours.

The resulting microgel emulsion had a solids content of about 38.51%. The particle size of the emulsion was determined as described above and was 0.147 microns. The microgel had about 44% of the amine functionality acid neutralized and 56.7% of the epoxy end groups capped with diketimine and 43.3% of the end groups capped with amino silane. The percent of insoluble microgel was determined by solvent extraction techniques and was 69.65%.

Example 5

An electrocoating composition was prepared according to Example 1 of U.S. Pat. No. 5,070,149 and then the following electrocoating baths 1-13 were formulated with the with each of the microgels prepared in Examples 1-4:

    ______________________________________                                         Elecrocoating            Corrosion Test -                                      Bath      % Microgel     Number of Rust Spots                                  ______________________________________                                         Bath No. 1                                                                               Control (0%)   97.3                                                            Microgel                                                             Bath No. 2                                                                               3% Microgel (Ex,.1)                                                                           91.6                                                  Bath No. 3                                                                               6.6% Microgel (Ex.1)                                                                          39.6                                                  Bath No. 4                                                                               9.9% Microgel (Ex.1)                                                                          0.0                                                   Bath No. 5                                                                               3% Microgel (Ex,.2)                                                                           64.1                                                  Bath No. 6                                                                               6.6% Microgel (Ex.2)                                                                          32.5                                                  Bath No. 7                                                                               9.9% Microgel (Ex.2)                                                                          0.0                                                   Bath No. 8                                                                               3.3% Microgel (Ex.3)                                                                          51.3                                                  Bath No. 9                                                                               6.6% Microgel (Ex.3)                                                                          22.7                                                  Bath No. 10                                                                              9.9% Microgel (Ex.3)                                                                          0.0                                                   Bath No. 11                                                                              3.3% Microgel (Ex.4)                                                                          74.9                                                  Bath No. 12                                                                              6.6% Microgel (Ex.4)                                                                          29.5                                                  Bath No. 13                                                                              9.9% Microgel (Ex.4)                                                                          0.0                                                   ______________________________________                                    

In the corrosion test used above, three separate sets of razor blades (10×2 cm with 38° blade angle) were electrocoated at 230 volts in each bath and the coating was baked at about 182° C. for 17 minutes to provide a coating having a dry film build of 0.8 mils (20.3 microns). Each of the razor blades was exposed five days to a standard salt spry test and the rust spots on each of the blades was counted and averaged for each set of three blades and the results are set forth above in the table.

The test results showed that there was a significant improvement in corrosion resistance for each bath containing the microgel in comparison to the control that did not contain microgel. In each case, the higher the amount of microgel a better the level corrosion resistance was noted. 

We claim:
 1. A cationic finely divided polymeric microgel having a particle size of about 0.01-6 microns dispersed in an aqueous medium for use in aqueous cationic electrocoating compositions: said polymeric microgel consisting essentially of a product produced by reacting an epoxy terminated poly epoxy hydroxy ether resin, a ketimine, a primary, secondary amine or mixtures thereof and amino silane to provide a resin having silanol groups and amino groups when in an aqueous medium; and said amino groups being neutralized with an organic acid to form cationic groups for water dispersibility and said silanol groups being condensed with hydroxy groups of the resin and other silanol groups of the resin thereby forming a crosslinked microgel.
 2. The microgel of claim 1 in which the ketimine is a diketimine and the amino silane is an amino alkyl trialkoxy silane.
 3. The microgel of claim 1 in which the poly epoxy hydroxy ether resin is a diglycidyl ether of a polyphenol extended with a polyol.
 4. The microgel of claim 3 in which about 20-90% of the glycidyl groups are reacted with a ketimine, a primary amine, a secondary amine or mixtures thereof and about 10-80% of the glycidyl groups are reacted with amino silane.
 5. The microgel of claim 4 in which the ketimine is diketimine and the amine is methylethanol amine and the amino silane is gamma-aminopropyl triethoxy silane.
 6. The microgel of claim 4 is which the ketimine is diketimine and amino silane is gamma-aminopropyl triethoxy silane.
 7. An aqueous electrocoating composition having a film forming binder of a basic polyepoxide/amine adduct resin containing amino groups and hydroxyl groups capable of reaction with isocyanate groups and a blocked polyisocyanate crosslinking agent containing about 0.1-20% by weight, based on the weight of the binder, of the microgel of claim
 1. 8. A process for forming an aqueous microgel which comprises the following steps:(1) reacting an epoxy terminated poly epoxy hydroxy ether resin with a ketimine, a primary amine, secondary amine or any mixtures thereof and an amino silane to form a resin with amino and silanol groups when in an aqueous medium; (2) neutralizing amino groups of the resin of step (1) with an organic acid and adding water to form a dispersion; (3) in the presence of a catalyst condensing the silanol groups with hydroxy groups or other silanol groups of the resin to form microgel which is dispersed in water.
 9. The process of claim 8 in which the reaction is with a ketimine and the ketimine is a diketimine and the amino silane is an amino alkyl trialkoxy silane.
 10. The process of claim 9 in which the amino silane is gamma-aminopropyl triethoxy silane.
 11. The process of claim 8 in which the poly epoxy hydroxy ether resin is a diepoxy polyhydroxy polyether resin extended with a polyol.
 12. The process of claim 8 in which about 20-90% of the epoxy groups are terminated with diketimine, primary amine, secondary amine or mixtures thereof and 10-80% of the epoxy groups are terminated with an amino silane. 